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Cyclopropene

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Cyclopropene
Skeletal formula of cyclopropene
Skeletal formula of cyclopropene with implicit hydrogens shown
Skeletal formula of cyclopropene with implicit hydrogens shown
Ball and stick model of cyclopropene
Ball and stick model of cyclopropene
Names
Systematic IUPAC name
Cyclopropene[1]
Identifiers
3D model (JSmol)
ChemSpider
MeSH cyclopropene
  • InChI=1S/C3H4/c1-2-3-1/h1-2H,3H2 ☒N
    Key: OOXWYYGXTJLWHA-UHFFFAOYSA-N ☒N
  • C1C=C1
Properties
C3H4
Molar mass 40.065 g·mol−1
Boiling point −36 °C (−33 °F; 237 K)
Thermochemistry
51.9-53.9 J K−1 mol−1
-2032--2026 kJ mol−1
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
☒N verify (what is checkY☒N ?)

Cyclopropene is an organic compound with the formula Template:Carbon3Template:Hydrogen4. It is the simplest cycloalkene. It has a triangular structure. Because the ring is highly strained, cyclopropene is both difficult to prepare and interesting to study.[2] The reduced length of the double bond compared to a single bond causes the angle opposite the double bond to narrow to about 51°[3] from the 60° angle found in cyclopropane. As with cyclopropane, the carbon–carbon bonding in the ring has increased p character: the alkene carbons use sp2.68 hybridization for the ring.[4]

Synthesis of cyclopropene and derivatives

Early syntheses

The first confirmed synthesis of cyclopropene, carried out by Dem'yanov and Doyarenko, involved the thermal decomposition of trimethylcyclopropylammonium hydroxide over platinized clay at 320–330 °C under a CO2 atmosphere. This reaction produces mainly trimethylamine and dimethylcyclopropyl amine, together with about 5% of cyclopropene. Cyclopropene can also be obtained in about 1% yield by thermolysis of the adduct of cycloheptatriene and dimethyl acetylenedicarboxylate.

Modern syntheses from allyl chlorides

Allyl chloride undergoes dehydrohalogenation upon treatment with the base sodium amide at 80 °C to produce cyclopropene in about 10% yield.[5]

CH2=CHCH2Cl + NaNH2 → C3H4 (cyclopropene) + NaCl + NH3

The major byproduct of the reaction is allylamine. Adding allyl chloride to sodium bis(trimethylsilyl)amide in boiling toluene over a period of 45–60 minutes produces the targeted compound in about 40% yield with an improvement in purity:[6]

CH2=CHCH2Cl + NaN(TMS)2 → C3H4 (cyclopropene) + NaCl + NH(TMS)2

1-Methylcyclopropene is synthesized similarly but at room temperature from methallylchloride using phenyllithium as the base:[7]

CH2=C(CH3)CH2Cl + LiC6H5 → CH3C3H3 (1-methylcylopropene) + LiCl + C6H6

Syntheses of derivatives

Treatment of nitrocyclopropanes with sodium methoxide eliminates the nitrite, giving the respective cyclopropene derivative. The synthesis of purely aliphatic cyclopropenes was first illustrated by the copper-catalyzed additions of carbenes to alkynes. In the presence of a copper sulfate catalyst, ethyl diazoacetate reacts with acetylenes to give cyclopropenes. 1,2-Dimethylcyclopropene-3-carboxylate arises via this method from 2-butyne. Copper has proved to be useful as a catalyst in a variety of cyclopropene syntheses. Copper sulfate and copper dust are among the more popular forms of copper used.Recently, Rhodium acetate has been used to synthesize derivatives of cyclopropene at room temperature and in high yields.

Reactions of cyclopropene

Studies on cyclopropene mainly focus on the consequences of its high ring strain. At 425 °C, cyclopropene isomerizes to methylacetylene (propyne).

C3H4 → H3CC≡CH

Attempted fractional distillation of cyclopropene at –36 °C (its predicted boiling point) results in polymerization. The mechanism is assumed to be a free-radical chain reaction, and the product, based on NMR spectra, is thought to be polycyclopropane.

Cyclopropene undergoes the Diels–Alder reaction with cyclopentadiene to give endo-tricyclo[3.2.1.02,4]oct-6-ene. This reaction is commonly used to check for the presence of cyclopropene, following its synthesis.[6]

  • Malvalic acid is a toxic cyclopropene fatty acid that occurs in cottonseed oil.
  • 1-Methylcyclopropene (1-MCP) is used to slow the ripening in fruits.[8][9]
  • Borirenes, phosphirenes, and silirenes are boron-, phosphorus-, and silicon-substituted cyclopropenes, with the formula RBC2R'2, RPC2R'2, and R2SiC2R'2.

References

  1. ^ "cyclopropene - Compound Summary". PubChem Compound. USA: National Center for Biotechnology Information. 27 March 2005. Identification and Related Records. Retrieved 9 October 2011.
  2. ^ "Review of the Chemistry of Cyclopropene Compounds". Chemical Reviews. 64: 497–525. 1964. doi:10.1021/cr60231a001. {{cite journal}}: Unknown parameter |authors= ignored (help)
  3. ^ "Structure of 3-cyanocyclopropene by microwave spectroscopy and ab initio molecular orbital calculations. Evidence for substituent-ring double bond interactions". J. Am. Chem. Soc. 109 (10): 2880–2884. 1987. doi:10.1021/ja00244a004. {{cite journal}}: Unknown parameter |authors= ignored (help)
  4. ^ Allen, F. H. (1982). "The geometry of small rings: Molecular geometry of cyclopropene and its derivatives". Tetrahedron. 38 (5): 645–655. doi:10.1016/0040-4020(82)80206-8.
  5. ^ "A Simple Synthesis of Cyclopropene". Journal of Organic Chemistry. 31: 638. 1966. doi:10.1021/jo01340a534. {{cite journal}}: Unknown parameter |authors= ignored (help)
  6. ^ a b Binger, P.; Wedermann, P.; Brinker, U. H. (2000). "Cyclopropene: A New Simple Synthesis and Its Diels-Alder reaction with Cyclopentadiene". Organic Syntheses. 77: 254{{cite journal}}: CS1 maint: multiple names: authors list (link); Collected Volumes, vol. 10, p. 231.
  7. ^ "An Efficient and Convenient Synthesis of 1-Methylcyclopropene". J. Org. Chem. 36: 1320. 1971. doi:10.1021/jo00808a041. {{cite journal}}: Unknown parameter |authors= ignored (help)
  8. ^ "Use of 1-MCP on Apples". Perishable Handling Quarterly (108). University of California: 12. 2001. {{cite journal}}: Unknown parameter |authors= ignored (help)
  9. ^ "Inhibition of ethylene action by 1-methylcyclopropene extends postharvest life of "Bartlett" pears". Postharvest Biology and Technology. 32 (2): 193–204. May 2004. doi:10.1016/j.postharvbio.2003.11.009. {{cite journal}}: Unknown parameter |authors= ignored (help)
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